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United States Patent |
5,695,917
|
Nelson
,   et al.
|
December 9, 1997
|
Combination of yellow filter dye and 4-equivalent pyrazolone magenta
coupler
Abstract
A photographic element contains a four-equivalent pyrazolone magenta
coupler and a yellow filter dye represented by Formula I.
##STR1##
wherein: A is an acidic nucleus selected from the group consisting of
benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene, 5-pyrazolone,
isooxazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin,
thiohydantoin, oxazolidindione, pyrazolidindione, indandione,
pyrazolopyridone, 1,2,3,4-tetrahydroquinolin-2,4-dione,
3-oxo-2,3-dihydrobenzo›d!thiophene-1,1-dioxide and
3-dicynaomethine-2,3-dihydroxybenzo›d!thiophene-1,1-dioxide;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups (including, for example,alkoxycarbonyl, amido and carboxyl);
Y represents non-metal atoms which form a five membered heterocyclic ring
optionally comprising a fused substituted or unsubstituted benzene ring;
and wherein the dye comprises at least one ionizable group with a pKa
value between 4-11 such as a carboxyl group, a sulfonamido group or a
sulfamoyl group.
Inventors:
|
Nelson; John Victor (Fairport, NY);
Helber; Margaret Jones (Rochester, NY);
Brick; Mary Christine (Webster, NY)
|
Assignee:
|
Eastman Kodak Company (Rochester, NY)
|
Appl. No.:
|
561677 |
Filed:
|
November 22, 1995 |
Current U.S. Class: |
430/522; 430/510; 430/517; 430/554 |
Intern'l Class: |
G03C 001/06; G03C 001/815; G03C 001/825 |
Field of Search: |
430/522,554,517,510,543
|
References Cited
U.S. Patent Documents
2533472 | Dec., 1950 | Keyes et al. | 430/522.
|
2538008 | Jan., 1951 | Keyes et al. | 260/465.
|
2538009 | Jan., 1951 | Keyes et al. | 95/8.
|
3627532 | Dec., 1971 | Depoorter et al. | 430/522.
|
4420555 | Dec., 1983 | Krueger et al. | 430/507.
|
4855221 | Aug., 1989 | Factor et al. | 430/510.
|
4857446 | Aug., 1989 | Diehl et al. | 430/510.
|
4861700 | Aug., 1989 | Shuttleworth et al. | 430/517.
|
4900653 | Feb., 1990 | Factor et al. | 430/522.
|
4923788 | May., 1990 | Shuttleworth et al. | 430/507.
|
4940654 | Jul., 1990 | Diehl et al. | 430/522.
|
4948717 | Aug., 1990 | Diehl et al. | 430/510.
|
4948718 | Aug., 1990 | Factor et al. | 430/522.
|
4950586 | Aug., 1990 | Diehl et al. | 430/507.
|
5213956 | May., 1993 | Diehl et al. | 430/522.
|
5213957 | May., 1993 | Adachi | 430/522.
|
5256528 | Oct., 1993 | Merkel et al. | 430/555.
|
5283165 | Feb., 1994 | Diehl et al. | 430/522.
|
5288600 | Feb., 1994 | Yamanouchi et al. | 430/522.
|
5296344 | Mar., 1994 | Jimbo et al. | 430/522.
|
5342743 | Aug., 1994 | Goto et al. | 430/522.
|
5449594 | Sep., 1995 | Ueda et al. | 430/522.
|
Foreign Patent Documents |
0 434 026 A1 | Dec., 1990 | EP.
| |
0 430 186 | Jun., 1991 | EP | .
|
0 524 598 A1 | Jan., 1993 | EP.
| |
0 529 737 A1 | Mar., 1993 | EP.
| |
0 543 921 | Mar., 1995 | EP | .
|
04 136 935 A | May., 1992 | JP.
| |
06 289 538 A | Oct., 1994 | JP.
| |
07 128 792 A | May., 1995 | JP.
| |
542 905 | Feb., 1942 | GB.
| |
695873 | Aug., 1953 | GB.
| |
760739 | Nov., 1956 | GB.
| |
WO 95 19169 A | Jul., 1995 | WO.
| |
Primary Examiner: Letscher; Geraldine
Attorney, Agent or Firm: Rice; Edith A.
Claims
What is claimed is:
1. A silver halide photographic element comprising at least one
four-equivalent pyrazolone magenta coupler and a yellow filter dye of
Formula I:
##STR11##
wherein: A is an acidic nucleus selected from the group consisting of
benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene, barbituric acid,
thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolidindione,
pyrazolidindione, indandione, pyrazolopyridone,
1,2,3,4-tetrahydroquinolin-2,4-dione,
3-oxo-2,3-dihydrobenzothiophene-1,1-dioxide and
3-dicyanomethine-2,3-dihydroxybenzothiophene-1,1-dioxide;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n=0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups;
Y represents non-metal atoms which form a five membered heterocyclic ring
optionally comprising a fused substituted or unsubstituted benzene ring;
and wherein the dye comprises at least one ionizable group with a pKa
value between 4-11.
2. A photographic element according to claim 1, wherein the four equivalent
magenta coupler is of the formula:
##STR12##
wherein: R.sup.8 is a substituted or unsubstituted aryl group;
R.sup.9 is an anilino, carbonamido, ureido, carbamoyl, alkoxy,
aryloxycarbonyl, alkoxycarbonyl, or N-heterocyclic group;
and wherein a ballasting group is incorporated into R.sup.8 and/or R.sup.9.
3. A photographic element according to claim 2, wherein the yellow filter
dye of Formula I is of Formula III:
##STR13##
wherein: A is an acidic nucleus selected from the group consisting of
benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene, barbituric acid,
thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolidindione,
pyrazolidindione, indandione, pyrazolopyridone,
1,2,3,4-tetrahydroquinolin-2,4-dione,
3-oxo-2,3-dihydrobenzothiophene-1,1-dioxide and
3-dicyanomethine-2,3-dihydroxybenzothiophene-1,1-dioxide;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups;
R.sup.3 is hydrogen or a substituent group; and wherein the dye comprises
at least one ionizable group with a pKa value between 4-11 such as a
carboxyl group, a sulfonamido group or a sulfamoyl group.
4. A photographic element according to claim 2, wherein the yellow filter
dye of Formula I is of Formula IV:
##STR14##
wherein: R.sup.4-6 each independently represents hydrogen or a substituent
group;
G is O or dicyanovinyl;
E is an electron withdrawing group;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups;
Y represents non-metal atoms which form a five membered heterocyclic ring
optionally comprising a fused substituted or unsubstituted benzene ring;
and wherein the dye comprises at least one ionizable group with a pKa
value between 4-11.
5. A photographic element according to claim 2, wherein the yellow filter
dye of Formula I is of Formula V:
##STR15##
wherein: R.sup.4-6 each independently represents a hydrogen or a
substituent group
G is 0 or dicyanovinyl;
E is an electron withdrawing group;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups;
R.sup.3 =hydrogen or a substituent group; and wherein the dye comprises at
least one ionizable group with a pKa value between 4-11 such as a carboxyl
group, a sulfonamido group or a sulfamoyl group.
Description
FIELD OF THE INVENTION
This invention relates to a photographic element comprising a yellow filter
dye and a four-equivalent pyrazolone magenta coupler.
BACKGROUND OF THE INVENTION
Photographic materials often contain layers sensitized to different regions
of the spectrum, such as red, blue, green, ultraviolet, infra-red, X-ray,
to name a few. A typical color photographic element contains a layer
sensitized to each of the three primary regions of the visible spectrum,
i.e., blue, green and red. All silver halide emulsions used in these
photographic elements have an intrinsic sensitivity to exposure by blue
light (light of a wavelength between 400 and 500 nm). Increased
sensitivity to blue light, along with sensitivity to green light or red
light, is imparted through the use of various sensitizing dyes adsorbed to
the silver halide grains. Exposure of green or red-sensitive emulsions by
blue light results in a significant degradation of the photographic
element's ability to accurately reproduce the colors of the original
scene. As a result, the control of blue light exposure within a silver
halide photographic element is a critical issue to the performance of
these elements. Therefore, a material that absorbs blue light is usually
coated between the blue sensitive layers and the remaining light sensitive
layers of the element to prevent blue light from exposing the non-blue
sensitive layers.
One commonly used blue light absorbing material is colloidal, or Carey-Lea,
silver (J. Kapecki and J. Rodgers, "Color Photography" in Kirk-Othmer
Encyclopedia of Chemical Technology--Fourth Edition, Volume 6, pp
965-1002, John Wiley and Sons, Inc., 1993). However, colloidal silver
absorbs some green light and tends to increase the fog of silver halide
emulsions in adjacent layers. The green light absorption results in a
speed loss that is corrected through the use of larger grain size
emulsions; however, this decreases image quality due to higher
granularity. The increased fog requires coating higher emulsion laydowns
or other corrective measures that have various costs associated with them.
Problem To Be Solved By The Invention
An alternative blue light absorbing material is a yellow filter dye such as
those disclosed in U.S. Pat. Nos. 2,538,008, 2,538,009 and 4,420,555, and
U.K. Patent Nos. 695,873 and 760,739. These dyes are often incorporated as
microcrystalline dye dispersions. U.S. Pat. Nos. 4,950,586, 4,948,718,
4,948,717, 4,940,654, 4,923,788, 4,900,653, 4,861,700, 4,857,446,
4,855,221, 5,213,956 and 5,213,957 and EP 430,186 disclose the use of
various dyes in solid particle dispersions. When properly designed, these
dyes reduce or eliminate the green speed losses and increased fog caused
by colloidal silver. However, we have discovered that when coated in a
photographic element that also contains a four-equivalent pyrazolone
magenta coupler, the existing yellow filter dyes may cause a yellow
print-out problem. This problem results from a reaction of the yellow
filter dye and the magenta coupler, either before or during the
photographic processing of the element, to form an initially colorless
intermediate. Thus, while the filter dye is completely decolorized by
photographic processing, when the processed photographic element is
exposed to light, such as display on a light table or illuminator, the
intermediate reacts further to form a yellow stain. Formation of the
yellow stain results in images with an objectionable yellow cast. It is
therefore desirable to provide a yellow filter dye that prevents the
formation of this yellow print-out while maintaining the existing
advantages of this type of dye. It is towards this end that the present
invention is directed.
SUMMARY OF THE INVENTION
The yellow print-out in a photographic element containing a yellow filter
dye and a four-equivalent pyrazolone magenta coupler can be prevented by
using certain yellow filter dyes. One aspect of this invention comprises a
photographic element comprising a four-equivalent pyrazolone magenta
coupler and a yellow filter dye represented by Formula I.
##STR2##
wherein: A is an acidic nucleus selected from the group consisting of
benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene, 5-pyrazolone,
isooxazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin,
thiohydantoin, oxazolidindione, pyrazolidindione, indandione,
pyrazolopyridone, 1,2,3,4-tetrahydroquinolin-2,4-dione,
3-oxo-2,3-dihydrobenzo›d!thiophene-1,1-dioxide and
3-dicynaomethine-2,3-dihydroxybenzo›d!thiophene-1,1-dioxide;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups (including, for example,alkoxycarbonyl, amido and carboxyl);
Y represents non-metal atoms which form a five membered heterocyclic ring
optionally comprising a fused substituted or unsubstituted benzene ring;
and wherein the dye comprises at least one ionizable group with a pKa
value between 4-11 such as a carboxyl group, a sulfonamido group or a
sulfamoyl group.
ADVANTAGEOUS EFFECT OF THE INVENTION
The problem of yellow print-out when yellow filter dyes are combined with
four-equivalent pyrazolone magenta couplers has not been addressed in the
prior art. The present invention identifies and offers a solution for this
problem.
DETAILED DESCRIPTION OF THE INVENTION
Four-equivalent pyrazolone magenta couplers are commonly used in
photographic elements. Preferred couplers are represented by Formula II
##STR3##
wherein: R.sup.8 is a substituted or unsubstituted aryl group;
R.sup.9 is an anilino, carbonamido, ureido, carbamoyl, alkoxy,
aryloxycarbonyl, alkoxycarbonyl, or N-heterocyclic group; and wherein a
ballasting group is incorporated into R.sup.8 and/or R.sup.9. A ballasting
group is a substituent that prevents substantial migration of the coupler
within the photographic element. Migration should be limited during both
shelf keeping and processing. Preferably, the ballasting groups are large
organic substituents containing at least 12, and more preferably at least
15, contiguous atoms and including substituted or unsubstituted alkyl,
aryl or aralkyl groups.
Representative examples of these magenta couplers are shown below.
##STR4##
In addition to the non-polymeric couplers described above, the magenta
coupler may also be a polymeric coupler if R.sup.8 or R.sup.9 is a
divalent or a more polyvalent group that forms an oligomer, such as a
dimer, or that connects the coupler skeleton to a polymeric main chain.
The four-equivalent pyrazolone magenta couplers are normally coated in the
green-light sensitive layers of the photographic element. However, they
may be coated in other layers as well.
Yellow filter dyes are normally coated in an interlayer above the
green-light sensitive layers where they are used to prevent blue-light
exposure of the underlying green and red-light sensitive layers. However,
they may be coated in other layers such as antihalation layers (for
blue-light protection) or blue-sensitive layers (for speed control or
increased acutance by reduction of light scatter). The yellow print-out
problem begins when the dye, or fragments of the dye formed during storage
or processing, react with the magenta coupler during processing. This
reaction may take place in the layer where the magenta coupler is coated
or in another layer, such as the layer where the yellow filter dye is
coated. Reaction in layers other than the magenta coupler containing layer
are possible because although the ballast group of the magenta coupler
prevents substantial migration, under some circumstances magenta couplers
may wander into other layers of the photographic element (European Patent
Specification 0 543 921 B1). The intermediate formed from this reaction is
colorless so that, immediately after processing, there is no undesired
stain and it appears that the yellow filter dye has been completely
decolorized and removed from the photographic element. However, if the
photographic element is then exposed to light, such as illumination on a
light box, the intermediate reacts further to form a yellow dye. This
yellow dye is different in chemical structure than the original yellow
filter dye. Its formation in the photographic element is highly
undesirable as it results in an image with a yellow cast. This yellow cast
is particularly noticeable in Dmin areas and light colored areas of the
image.
The dyes of the present invention do not cause any yellow print-out when
coated in a photographic element containing four-equivalent pyrazolone
couplers. Formula I is described in detail as follows.
A in Formula I represents an acidic nucleus selected from the group
consisting of benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene,
5-pyrazolone, isooxazolone, barbituric acid, thiobarbituric acid,
rhodanine, hydantoin, thiohydantoin, oxazolidindione, pyrazolidindione,
indandione, pyrazolopyridone, 1,2,3,4-tetrahydroquinolin-2,4-dione,
3-oxo-2,3-dihydrobenzo›d!thiophene-1,1-dioxide and
3-dicynaomethine-2,3-dihydroxybenzo›d!thiophene-1,1-dioxide. The acidic
nucleus is preferably selected from the group consisting of
benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene, 5-pyrazolone,
isooxazolone, barbituric acid, oxazolidindione, pyrazolidindione,
indandione and pyrazolopyridone nuclei. The acidic nucleus may have a
subsituent.
L.sup.1, L.sup.2 and L.sup.3 in Formula I each independently represents
substituted or unsubstituted methine groups. Preferable substitutents for
L.sup.1-3 are alkyl groups of between 1 and 6 carbons. Other useful
substituents for L.sup.1-3 include those listed below for R.sup.3. In
Formula I, n represents 0 or 1 with 0 being preferred.
Y in Formula I represents non-metal atoms which may be assembled to form a
five membered heterocylic ring optionally comprising a fused substituted
or unsubstituted benzene ring. Heterocyclic rings formed by Y are
preferably selected from the group consisting of pyrrole, indole,
pyrazole, pyrazolopyrimidone and benzindole. Dyes in which Y is an indole
ring, a benzindole ring or a pyrrole are particularly preferred. R.sup.1
and R.sup.2 each independently represents hydrogen, alkyl, aryl or acyl
groups (including, for example, alkoxycarbonyl, amido and carboxy).
The dye described by Formula I also comprises at least one ionizable group
with a pKa value between 4-11 such as a carboxyl group, a sulfonamido
group or a sulfamoyl group. Preferably, this group is a carboxy
(--CO.sub.2 H) or sulfonamido group (-NHSO.sub.2 R.sup.10, where R.sup.10
is a substituted alkyl or aryl group as described for R.sup.3 below).
The dyes of Formula I may be incorporated into the photographic element in
any of the ways known in the art, but preferably as a dispersion of
microcrystalline dye.
In a preferred/another embodiment, the objectives and advantages of the
invention are met by photographic elements wherein the dye according to
Formula I has Formula III:
##STR5##
wherein: A is an acidic nucleus selected from the group consisting of
benzoylacetonitrile, 2-phenyl-1,1,3-tricyanopropene, 5-pyrazolone,
isooxazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin,
thiohydantoin, oxazolidindione, pyrazolidindione, indandione,
pyrazolopyridone, 1,2,3,4-tetrahydroquinolin-2,4-dione,
3-oxo-2,3-dihydrobenzo›d!thiophene-1,1-dioxide and
3-dicynaomethine-2,3-dihydroxybenzo›d!thiophene-1,1-dioxide;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups (including, for example, alkoxycarbonyl, amido and carboxyl);
R.sup.3 =hydrogen or a substituent group; and wherein the dye comprises at
least one ionizable group with a pKa value between 4-11 such as a carboxyl
group, a sulfonamido group or a sulfamoyl group.
The groups A, L.sup.1, L.sup.2, L.sup.3, R.sup.1, and R.sup.2 are described
in greater detail above. The R.sup.3 substituent group in Formula III can
be substituted or unsubstituted alkyl, substituted or unsubstituted aryl
or arlyoxy, or may be one of the following subsituents including, for
example, hydrogen, halogen, cyano, amino, alkoxy, alkoxycarbonyl, amido,
acyl, alkylamino, carboxy, sulfonamido, sulfamoyl or hydroxy. When R.sup.3
is an alkyl or aryl group, it may be optionally substituted with one of
the substituents listed above. The alkyl or aryl groups may be substituted
with any of a number of substituents as is known in the art, other than
those such as sulfo substituents, that would tend to increase the
solubility of the dye so much as to cause it to become soluble at coating
pH's. Examples of alkyl groups include methyl, ethyl, n-propyl, n-hexyl or
isohexyl. Examples of substituted alkyl groups include, for example,
methoxyethyl, hydroxymethyl, etc. Examples of alkoxy groups include, for
example, methoxy, ethoxy, butoxy. Examples of aryl groups include phenyl,
naphthyl, anthracenyl, pyridyl and styryl. Examples of substituted aryl
groups include, for example, tolyl, m-cholrophenyl,
p-methanesulfonylphenyl, etc.
In another preferred embodiment, the objectives and advantages of the
invention are met by photographic elements wherein the dye according to
Formula I has Formula IV:
##STR6##
wherein:
R.sup.4-6 =each independently represents hydrogen or a substituent group;
G is O or dicyanovinyl (--C(CN).sub.2);
E is an electron withdrawing group;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups (including, for example, alkoxycarbonyl, amido and carboxyl);
Y represents non-metal atoms which form a five membered heterocyclic ring
optionally comprising a fused substituted or unsubstituted benzene ring;
and wherein the dye comprises at least one ionizable group with a pKa
value between 4-11 such as a carboxyl group, a sulfonamido group or a
sulfamoyl group.
The groups L.sup.1, L.sup.2, L.sup.3, R.sup.1, R.sup.2 and Y are described
in greater detail above. The substituent groups R.sup.4, R.sup.5 and
R.sup.6 can each independently be any of the groups described for R.sup.3
above. The group E in Formula III is an electron withdrawing group.
Electron withdrawing groups in organic compounds are well known in the
art, such as described by March, Advanced Organic Chemistry, 3rd Ed., p.
238, the disclosure of which is incorporated herein by reference in its
entirety. Examples of such groups include cyano, acyl, aminocarbonyl and
alkoxycarbonyl. In a preferred embodiment, E is cyano.
In another preferred embodiment, the objectives and advantages of the
invention are met by photographic elements wherein the dye according to
Formula I has Formula V:
##STR7##
wherein: R.sup.4-6 each independently represents a hydrogen or a
substituent group;
G is O or dicyanovinyl (--C(CN).sub.2);
E is an electron withdrawing group;
L.sup.1-3 each independently represents a substituted or unsubstituted
methine group;
n is 0 or 1;
R.sup.1-2 each independently represents hydrogen or an alkyl, aryl or acyl
groups (including, for example, alkoxycarbonyl, amido and carboxyl);
R.sup.3 =hydrogen or a substituent group; and wherein the dye comprises at
least one ionizable group with a pKa value between 4-11 such as a carboxyl
group, a sulfonamido group or a sulfamoyl group.
The groups R.sup.4, R.sup.5, R.sup.6, G, E, L.sup.1, L.sup.2, L.sup.3,
R.sup.1, R.sup.2 and R.sup.3 are described in greater detail above.
Representative examples of the yellow filter dyes of the present invention
are shown below.
##STR8##
The yellow filter dyes of the present invention described in Table I refer
to the generic structure shown below.
##STR9##
TABLE I
__________________________________________________________________________
YFD-
R.sup.4
R.sup.5
R.sup.6
R.sup.1
R.sup.2
R.sup.7
R.sup.3
G
__________________________________________________________________________
4 NHSO.sub.2 CH.sub.3
H H H H H H O
5 COOH H H H H H H O
6 NHSO.sub.2 CH.sub.3
H H H H H H C(CN).sub.2
7 NHSO.sub.2 C.sub.3 H.sub.7
H H H H H H O
8 NHSO.sub.2 CH.sub.3
H H CH.sub.3
H H W O
9 NHSO.sub.2 C.sub.2 H.sub.5
H H CH.sub.3
H H H O
10 NHSO.sub.2 C.sub.3 H.sub.7
H H CH.sub.3
H H H O
11 NHSO.sub.2 C.sub.4 H.sub.9
H H CH.sub.3
H H H O
12 NHSO.sub.2 C.sub.4 H.sub.9
H H H H H CO.sub.2 CH.sub.3
O
13 NHSO.sub.2 CH.sub.3
H H H CH.sub.3
H H O
14 NHSO.sub.2 CH.sub.3
H H CH.sub.3
H H H C(CN)2
15 NHSO.sub.2 CH.sub.3
H H H H H CO.sub.2 CH.sub.3
O
16 COOH H H H H H H C(CN)2
17 H H H H H H H O
18 H NHSO.sub.2 CH.sub.3
H CH.sub.3
H H H O
19 NHSO.sub.2 CH.sub.3
H H CH.sub.3
CH.sub.3
H H O
20 H NHSO.sub.2 CH.sub.3
H H H H H O
21 CO.sub.2 CH.sub.3
H H H H H H O
22 H COOH H H H H H
23 H COOH H CH.sub.3
CH.sub.3
H H O
24 COOH H H H H CH.sub.3
H O
25 COOH H H H H H COOH O
26 NHSO.sub.2 CH.sub.3
H H H H H COOH O
27 OH H H H H H H O
28 OH OH H CH.sub.3
CH.sub.3
H H O
29 SO.sub.2 NHCH.sub.3
H H H H H CO.sub.2 CH.sub.3
O
30 OH H OH H H H H O
__________________________________________________________________________
The filter dyes of this invention can be incorporated into the photographic
element in any of the ways known in the art. They may be added directly
to, or dispersed in film forming polymeric vehicles and/or binders, as is
well known in the art. These include both naturally occurring and
synthetic binders, such as gelatin and gelatin derivatives, polyvinyl
alcohols, acrylamide polymers, polyvinyl acetates, polyacrylates and the
like. In certain instances, especially where the dye is mobile (e.g., a
dye with one or more SO.sub.3 --constituents) it may be advantageous to
use the dye in combination with a mordant, such as polyvinylimidazole and
polyvinylpyridine, to aid in immobilizing the dye. The technology of
mordanting dyes is well known in the art, and is described in further
detail in Jones et al U.S. Pat. No. 3,282,699 and Heseltine et al U.S.
Pat. No. 3,255,693 and 3,483,779. An oil-in-water dispersion of the dye
may be prepared by dissolving the dye in an organic liquid, forming a
premix with an aqueous phase containing dispersing aids such as
water-soluble surfactants, polymers and film forming binders such as
gelatin, and passing the premix through a mill until the desired particle
size is obtained. The mill can be any high energy device such as a colloid
mill, high pressure homogenizer, ultrasonic device, or the like.
Preparation of conventional oil-in-water dispersions are well known in the
art and are described in further detail in Jelly and Vittum U.S. Pat. No.
2,322,027. The dyes can also be loaded into a latex polymer, either during
or after polymerization, and the latex can be dispersed in a binder.
Additional disclosure in loaded latexes can be found in Milliken U.S. Pat.
No. 3,418,127.
In a preferred embodiment, the dye is dispersed in the binder in the form
of a solid particle dispersion. Such dispersions are formed by either
milling the dye in solid form until the desired particle size range is
reached, or by precipitating the dye directly in the form of a solid
particle dispersion. In the case of solid particle milling dispersal
methods, a coarse aqueous premix, containing the filter dye and water, and
optionally, any desired combination of water soluble surfactants and
polymers, is made, and added to this premix prior to the milling
operation. The resulting mixture is then loaded into a mill. The mill can
be, for example, a ball mill, media mill, jet mill, attritor mill,
vibratory mill, or the like. The mill is charged with the appropriate
milling media such as, for example, beads of silica, silicon nitride,
sand, zirconium oxide, yttria-stabilized zirconium oxide, alumina,
titanium, glass, polystyrene, etc. The bead sizes typically range from
0.25 to 3.0 mm in diameter, but smaller media may be used if desired. The
solid dye particles in the slurry are subjected to repeated collisions
with the milling media, resulting in crystal fracture and consequent
particle size reduction. The solid particle dispersions of the dye should
have an average particle size of 0.01 to about 10 microns, preferably 0.05
to about 5 microns, and more prefereable about 0.05 to about 3 microns.
Most preferably, the solid particles are of sub-micron average size. In
the case of pH precipitation techniques, an aqueous solution of the dye is
made at relatively high pH then the pH is lowered to cause precipitation
of the dye. The aqueous dispersion can further contain appropriate
surfactants and polymers previously disclosed for use in making pH
precipitated dispersions. For solvent precipitation, a solution of the dye
is made in some water miscible, organic solvent. The solution of the dye
is added to an aqueous solution containing appropriate surfactants and
polymers to cause precipitation as previously disclosed for use in making
solvent precipitated dispersions.
Surfactants and other additional conventional addenda may also be used in
the dispersing process described herein in accordance with prior art solid
particle dispersing procedures. Such surfactants, polymers and other
addenda are disclosed in U.S. Pat. Nos. 5,468,598, 5,300,394, 5,278,037,
4,006,025, 4,924,916, 4,294,917, 4,940,654, 4,950,586, 4,927,744,
5,279,931, 5,158,863, 5,135,844, 5,091,296, 5,089,380, 5,103,640,
4,990,431,4,970,139, 5,256,527, 5,015,564, 5,008,179, 4,957,857, and
2,870,012, British Patent specifications Nos. 1,570,362 and 1,131,179
referenced above, the disclosures of with are hereby incorporated by
reference, in the dispersing process of the filter dyes.
Additional surfactants or other water soluble polymers may be added after
formation of the filter dye dispersion, before or after subsequent
addition of the small particle dispersion to an aqueous coating medium for
coating onto a photographic element support. The aqueous medium preferably
contains other compounds such as stabilizers and dispersants, for example,
additional anionic nonionic, zwitterionic, or cationic surfactants, and
water soluble binders such as gelatin as is well known in the photographic
element art. The aqueous coating medium may further contain other
dispersion or emulsions of compounds useful in photography.
The photographic element of this invention is typically a multicolor
element. Multicolor elements contain dye image-forming units sensitive to
each of the three primary regions of the spectrum. Each unit can be
comprised of a single emulsion layer or of multiple emulsion layers
sensitive to a given region of the spectrum. The layers of the element,
including the layers of the image-forming units, can be arranged in
various orders as known in the art. In an alternative format, the
emulsions sensitive to each of the three primary regions of the spectrum
can be disposed as a single segmented layer.
A typical multicolor photographic element comprises a support bearing a
cyan dye image-forming unit comprised of at least one red-sensitive silver
halide emulsion layer having associated therewith at least one cyan
dye-forming coupler, a magenta dye image-forming unit comprising at least
one green-sensitive silver halide emulsion layer having associated
therewith at least one magenta dye-forming coupler, and a yellow dye
image-forming unit comprising at least one blue-sensitive silver halide
emulsion layer having associated therewith at least one yellow dye-forming
coupler. The element can contain additional layers, such as filter layers,
interlayers, overcoat layers, subbing layers, and the like. All of these
can be coated on a support which can be transparent or reflective (for
example, a paper support).
Photographic elements of the present invention may also usefully include a
magnetic recording material as described in Research Disclosure, Item
34390, November 1992, or a transparent magnetic recording layer such as a
layer containing magnetic particles on the underside of a transparent
support as in U.S. Pat. No. 4,279,945 and U.S. Pat. No. 4,302,523. The
element typically will have a total thickness (excluding the support) of
from 5 to 30 microns. While the order of the color sensitive layers can be
varied, they will normally be red-sensitive, green-sensitive and
blue-sensitive, in that order on a transparent support, (that is, blue
sensitive furthest from the support) and the reverse order on a reflective
support being typical.
The present invention also contemplates the use of photographic elements of
the present invention in what are often referred to as single use cameras
(or "film with lens" units). These cameras are sold with film preloaded in
them and the entire camera is returned to a processor with the exposed
film remaining inside the camera. Such cameras may have glass or plastic
lenses through which the photographic element is exposed.
In the following discussion of suitable materials for use in elements of
this invention, reference will be made to Research Disclosure, September
1994, Number 365, Item 36544, which will be identified hereafter by the
term "Research Disclosure I." The Sections hereafter referred to are
Sections of the Research Disclosure I unless otherwise indicated. All
Research Disclosures referenced are published by Kenneth Mason
Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire
P010 7DQ, ENGLAND. The foregoing references and all other references cited
in this application, are incorporated herein by reference.
The silver halide emulsions employed in the photographic elements of the
present invention may be negative-working, such as surface-sensitive
emulsions or unfogged internal latent image forming emulsions, or positive
working emulsions of internal latent image forming emulsions (that are
either fogged in the element or fogged during processing). Suitable
emulsions and their preparation as well as methods of chemical and
spectral sensitization are described in Sections I through V. Color
materials and development modifiers are described in Sections V through
XX. Vehicles which can be used in the photographic elements are described
in Section II, and various additives such as brighteners, antifoggants,
stabilizers, light absorbing and scattering materials, hardeners, coating
aids, plasticizers, lubricants and matting agents are described, for
example, in Sections VI through XIII. Manufacturing methods are described
in all of the sections, layer arrangements particularly in Section XI,
exposure alternatives in Section XVI, and processing methods and agents in
Sections XIX and XX.
With negative working silver halide a negative image can be formed.
Optionally a positive (or reversal) image can be formed although a
negative image is typically first formed.
The photographic elements of the present invention may also use colored
couplers (e.g. to adjust levels of interlayer correction) and masking
couplers such as those described in EP 213 490; Japanese Published
Application 58-172,647; U.S. Pa. No. 2,983,608; German Application DE
2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S.
Pat. No. 4,070,191 and German Application DE 2,643,965. The masking
couplers may be shifted or blocked.
The photographic elements may also contain materials that accelerate or
otherwise modify the processing steps of bleaching or fixing to improve
the quality of the image. Bleach accelerators described in EP 193 389; EP
301 477; U.S. Pat. No. 4,163,669; U.S. Pat. No. 4,865,956; and U.S. Pat.
No. 4,923,784 are particularly useful. Also contemplated is the use of
nucleating agents, development accelerators or their precursors (UK Patent
2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. Pat. No.
4,859,578; U.S. Pat. No. 4,912,025); antifogging and anti color-mixing
agents such as derivatives of hydroquinones, aminophenols, amines, gallic
acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non
color-forming couplers.
The elements may also contain filter dye layers comprising colloidal silver
sol or yellow and/or magenta filter dyes and/or antihalation dyes
(particularly in an undercoat beneath all light sensitive layers or in the
side of the support opposite that on which all light sensitive layers are
located) either as oil-in-water dispersions, latex dispersions or as solid
particle dispersions. Additionally, they may be used with "smearing"
couplers (e.g. as described in U.S. Pat. No. 4,366,237; EP 096 570; U.S.
Pat. No. 4,420,556; and U.S. Pat. No. 4,543,323.) Also, the couplers may
be blocked or coated in protected form as described, for example, in
Japanese Application 61/258,249 or U.S. Pat. No. 5,019,492.
The photographic elements may further contain other image-modifying
compounds such as "Developer Inhibitor-Releasing" compounds (DIR's).
Useful additional DIR's for elements of the present invention, are known
in the art and examples are described in U.S. Pat. Nos. 3,137,578;
3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506;
3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984;
4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437;
4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634;
4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601;
4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179;
4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835;
4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB
2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE
3,644,416 as well as the following European Patent Publications: 272,573;
335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212;
377,463; 378,236; 384,670; 396,486; 401,612; 401,613.
DIR compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR)
Couplers for Color Photography," C. R. Barr, J. R. Thirtle and P. W.
Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969),
incorporated herein by reference.
It is also contemplated that the concepts of the present invention may be
employed to obtain reflection color prints as described in Research
Disclosure, November 1979, Item 18716, available from Kenneth Mason
Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire
P0101 7DQ, England, incorporated herein by reference. The emulsions and
materials to form elements of the present invention, may be coated on pH
adjusted support as described in U.S. Pat. No. 4,917,994; with epoxy
solvents (EP 0 164 961); with additional stabilizers (as described, for
example, in U.S. Pat. No. 4,346,165; U.S. Pat. No. 4,540,653 and U.S. Pat.
No. 4,906,559); with ballasted chelating agents such as those in U.S. Pat.
No. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium;
and with stain reducing compounds such as described in U.S. Pat. No.
5,068,171 and U.S. Pat. No. 5,096,805. Other compounds useful in the
elements of the invention are disclosed in Japanese Published Applications
83-09,959; 83-62,586; 90-072,629, 90-072,630; 90-072,632; 90-072,633;
90-072,634; 90-077,822; 90-078,229; 90-078,230; 90-079,336; 90-079,338;
90-079,690; 90-079,691; 90-080,487; 90-080,489; 90-080,490; 90-080,491;
90-080,492; 90-080,494; 90-085,928; 90-086,669; 90-086,670; 90-087,361;
90-087,362; 90-087,363; 90-087,364; 90-088,096; 90-088,097; 90-093,662;
90-093,663; 90-093,664; 90-093,665; 90-093,666; 90-093,668; 90-094,055;
90-094,056; 90-101,937; 90-103,409; 90-151,577.
The silver halide used in the photographic elements may be silver
iodobromide, silver bromide, silver chloride, silver chlorobromide, silver
chloroiodobromide, and the like. For example, the silver halide used in
the photographic elements of the present invention may contain at least
90% silver chloride or more (for example, at least 95%, 98%, 99% or 100%
silver chloride). In the case of such high chloride silver halide
emulsions, some silver bromide may be present but typically substantially
no silver iodide. Substantially no silver iodide means the iodide
concentration would be no more than 1%, and preferably less than 0.5 or
0.1%. In particular, in such a case the possibility is also contemplated
that the silver chloride could be treated with a bromide source to
increase its sensitivity, although the bulk concentration of bromide in
the resulting emulsion will typically be no more than about 2 to 2.5% and
preferably between about 0.6 to 1.2% (the remainder being silver
chloride). The foregoing % figures are mole %.
The type of silver halide grains preferably include polymorphic, cubic, and
octahedral. The grain size of the silver halide may have any distribution
known to be useful in photographic compositions, and may be either
polydipersed or monodispersed.
Tabular grain silver halide emulsions may also be used. Tabular grains are
those with two parallel major faces each clearly larger than any remaining
grain face and tabular grain emulsions are those in which the tabular
grains account for at least 30 percent, more typically at least 50
percent, preferably >70 percent and optimally >90 percent of total grain
projected area. The tabular grains can account for substantially all (>97
percent) of total grain projected area. The tabular grain emulsions can be
high aspect ratio tabular grain emulsions--i.e., ECD/t>8, where ECD is the
diameter of a circle having an area equal to grain projected area and t is
tabular grain thickness; intermediate aspect ratio tabular grain
emulsions--i.e., ECD/t=5 to 8; or low aspect ratio tabular grain
emulsions--i.e., ECD/t=2 to 5. The emulsions typically exhibit high
tabularity (T), where T (i.e., ECD/t.sup.2)>25 and ECD and t are both
measured in micrometers (.mu.m). The tabular grains can be of any
thickness compatible with achieving an aim average aspect ratio and/or
average tabularity of the tabular grain emulsion. Preferably the tabular
grains satisfying projected area requirements are those having thicknesses
of <0.3 .mu.m, thin (<0.2 .mu.m) tabular grains being specifically
preferred and ultrathin (<0.07 .mu.m) tabular grains being contemplated
for maximum tabular grain performance enhancements. When the native blue
absorption of iodohalide tabular grains is relied upon for blue speed,
thicker tabular grains, typically up to 0.5 .mu.m in thickness, are
contemplated.
High iodide tabular grain emulsions are illustrated by House U.S. Pat. No.
4,490,458, Maskasky U.S. Pat. No. 4,459,353 and Yagi et al EPO 0 410 410.
Tabular grains formed of silver halide(s) that form a face centered cubic
(rock salt type) crystal lattice structure can have either {100} or {111}
major faces. Emulsions containing {111} major face tabular grains,
including those with controlled grain dispersities, halide distributions,
twin plane spacing, edge structures and grain dislocations as well as
adsorbed {111} grain face stabilizers, are illustrated in those references
cited in Research Disclosure I, Section I.B.(3) (page 503).
The silver halide grains to be used in the invention may be prepared
according to methods known in the art, such as those described in Research
Disclosure I and James, The Theory of the Photographic Process. These
include methods such as ammoniacal emulsion making, neutral or acidic
emulsion making, and others known in the art. These methods generally
involve mixing a water soluble silver salt with a water soluble halide
salt in the presence of a protective colloid, and controlling the
temperature, pAg, pH values, etc, at suitable values during formation of
the silver halide by precipitation.
The silver halide to be used in the invention may be advantageously
subjected to chemical sensitization with noble metal (for example, gold)
sensitizers, middle chalcogen (for example, sulfur) sensitizers, reduction
sensitizers and others known in the art. Compounds and techniques useful
for chemical sensitization of silver halide are known in the art and
described in Research Disclosure I and the references cited therein.
The photographic elements of the present invention, as is typical, provide
the silver halide in the form of an emulsion. Photographic emulsions
generally include a vehicle for coating the emulsion as a layer of a
photographic element. Useful vehicles include both naturally occurring
substances such as proteins, protein derivatives, cellulose derivatives
(e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as
cattle bone or hide gelatin, or acid treated gelatin such as pigskin
gelatin), gelatin derivatives (e.g., acetylated gelatin, phthalated
gelatin, and the like), and others as described in Research Disclosure I.
Also useful as vehicles or vehicle extenders are hydrophilic
water-permeable colloids. These include synthetic polymeric peptizers,
carriers, and/or binders such as poly(vinyl alcohol), poly(vinyl lactams),
acrylamide polymers, polyvinyl acetals, polymers of alkyl and sulfoalkyl
acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides,
polyvinyl pyridine, methacrylamide copolymers, and the like, as described
in Research Disclosure I. The vehicle can be present in the emulsion in
any amount useful in photographic emulsions. The emulsion can also include
any of the addenda known to be useful in photographic emulsions. These
include chemical sensitizers, such as active gelatin, sulfur, selenium,
tellurium, gold, platinum, palladium, iridium, osmium, rhenium,
phosphorous, or combinations thereof. Chemical sensitization is generally
carried out at pAg levels of from 5 to 10, pH levels of from 5 to 8, and
temperatures of from 30 to 80.degree. C., as described in Research
Disclosure I, Section IV (pages 510-511) and the references cited therein.
The silver halide may be sensitized by sensitizing dyes by any method known
in the art, such as described in Research Disclosure I. The dye may be
added to an emulsion of the silver halide grains and a hydrophilic colloid
at any time prior to (e.g., during or after chemical sensitization) or
simultaneous with the coating of the emulsion on a photographic element.
The dyes may, for example, be added as a solution in water or an alcohol.
The dye/silver halide emulsion may be mixed with a dispersion of color
image-forming coupler immediately before coating or in advance of coating
(for example, 2 hours).
Photographic elements of the present invention are preferably imagewise
exposed using any of the known techniques, including those described in
Research Disclosure I, section XVI. This typically involves exposure to
light in the visible region of the spectrum, and typically such exposure
is of a live image through a lens, although exposure can also be exposure
to a stored image (such as a computer stored image) by means of light
emitting devices (such as light emitting diodes, CRT and the like).
Photographic elements comprising the composition of the invention can be
processed in any of a number of well-known photographic processes
utilizing any of a number of well-known processing compositions,
described, for example, in Research Disclosure I, or in T. H. James,
editor, The Theory of the Photographic Process, 4th Edition, Macmillan,
N.Y., 1977. In the case of processing a negative working element, the
element is treated with a color developer (that is one which will form the
colored image dyes with the color couplers), and then with a oxidizer and
a solvent to remove silver and silver halide. In the case of processing a
reversal color element, the element is first treated with a black and
white developer (that is, a developer which does not form colored dyes
with the coupler compounds) followed by a treatment to fog silver halide
(usually chemical fogging or light fogging), followed by treatment with a
color developer. Preferred color developing agents are
p-phenylenediamines. Especially preferred are:
4-amino N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N-ethyl-N-(.beta.-(methanesulfonamido) ethylaniline
sesquisulfate hydrate,
4-amino- 3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)aniline sulfate,
4-amino-3-.beta.-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride
and
4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
Development is followed by bleach-fixing, to remove silver or silver
halide, washing and drying.
The practice of the invention is described in detail below with reference
to specific illustrative examples, but the invention is not to be
construed as being limited thereto. In the examples the filter dye
dispersions were prepared by the following procedures.
All filter dyes except FD-2 were dispersed by the following procedure:
A slurry containing 2.4 g dye, 1.92 g of a 10% aqueous solution of Luviskol
K-30 polyvinylpyrrolidone (BASF), 2.15 g of a 6.7% aqueous solution of
TX200 octylphenoxy ethylene oxide sulfonate (Union Carbide) and 17.53 g of
distilled water was added to a 120 ml glass jar with 60 ml of 1.8 mm
zirconium oxide ceramic beads. The jar was placed on a SWECO vibratory
mill for 6 days. After milling, the final slurry particle size was less
than 1 micron, and the slurry was diluted to a concentration of 5% dye
with distilled water.
Filter dye FD-2 was dispersed by the following procedure:
A solid particle dispersion was prepared by circulating a slurry containing
36% dye, 3.6% TX200 octylphenoxy ethylene oxide sulfonate (Union Carbide)
and 61.4% distilled water through a Netzsch 60 L media mill containing 54
L of 0.4 SEPR zirconium silicate ceramic beads until the final dispersion
particle size was less than 1 micron. After milling, the slurry was
diluted to a concentration of 5% dye and 7% gelatin with distilled water
and deionized gelatin.
EXAMPLE 1
On a cellulose triacetate film support provided With a subbing layer was
coated each layer having the composition set forth below to prepare a test
format which was designated sample 101. The test format consists of a
layer incorporating a four-equivalent equivalent pyrazolone magenta
coupler and a separate layer incorporating a yellow filter dye. The test
format will therefore provide a model of the light induced yellowing
problem observed in photographic elements containing both yellow filter
dyes and four-equivalent pyrazolone magenta couplers. In the composition
of the layers, the coating amounts are shown as g/m.sup.2.
______________________________________
First Layer: Magenta Coupler Layer
Magenta Coupier M-1 1.24
Dispersed in Solvent S-2
0.62
Gelatin 1.88
Second Layer: Yellow Filter Dye Layer
Gelatin 0.61
Third Layer: Overcoat Layer
Gelatin 2.15
Hardener H-1 0.08
______________________________________
Samples 102 to 111 were prepared in the same manner as described above for
Sample 101 except for the addition of 0.22 g/m.sup.2 of the yellow filter
dye listed in Table I to the Second Layer. Sample 112 was prepared in the
same manner as described above for Sample 102 except that magenta coupler
M-1 was omitted from the First Layer.
Each of the samples thus prepared was cut into a 35 mm width strip. The
samples were processed using standard Kodak E-6 processing solutions and
methods. The Status A blue density was then measured for each sample. The
samples were placed on a light box for 24 hours. The Status A blue density
was then re-measured for each sample. The density values before and after
the light box treatment, and the delta density, are tabulated in Table II.
TABLE II
______________________________________
Starting Ending
Deita
Sample Yellow Filter Dye
Density Density
Density
______________________________________
101 None (Check) 0.08 0.08 0
102 FD-2 (Comparison)
0.08 0.13 0.05
103 FD-3 (Comparison)
0.09 0.13 0.04
104 FD-4 (Comparison)
0.09 0.11 0.02
105 YFD-1 (Invention)
0.08 0.08 0
106 YFD-2 (Invention)
0.08 0.08 0
107 YFD-3 (Invention)
0.08 0.08 0
108 YFD-4 (Invention)
0.08 0.08 0
109 YFD-5 (Invention)
0.08 0.08 0
110 YFD-6 (Invention)
0.08 0.08 0
111 YFD-7 (Invention)
0.10 0.10 0
112 YFD-2 without M-1
0.07 0.07 0
(Check)
______________________________________
The check samples 101 and 112 demonstrate that unless both a comparison
yellow filter dye and the magenta coupler are present there is no increase
in blue density after light box treatment. From the results shown in Table
II it is clear that the samples using the yellow filter dyes of the
present invention exhibit no increase in blue density after the light box
treatment. The comparison yellow filter dyes, which fall outside the scope
of the present invention, exhibit an increased blue density.
EXAMPLE 2
On a cellulose triacetate support provided with a subbing layer was coated
each layer having the composition set forth below to prepare a multilayer
color photographic light-sensitive material which was designated sample
201. In the composition of the layers, the coating amounts are shown as
g/m.sup.2.
______________________________________
First Layer: Antihalation Layer
Black Colloidal Silver 0.43 (as silver)
UV Dye UV-1 0.04
Dispersed in Solvent S-1
0.04
Gelatin 2.44
Second Layer: Intermediate Layer
Gelatin 1.22
Third Layer: Slow Red Sensitive Layer
Silver Iodobromide Emuision
0.25 (as silver)
tabular emuision (13:1 aspect ratio)
3% bulk iodide
spectrally sensitized with dyes SD-1 and SD-2
Silver Iodobromide Emulsion
0.20 (as silver)
tabular emulsion (6:1 aspect ratio)
4% bulk iodide
spectrally sensitized with dyes SD-1 and SD-2
Silver Iodobromide Emulsion
0.12 (as silver)
0.15.mu. equivalent spherical diameter
4.8% bulk iodide
spectrally sensitized
Fine Grain Silver Bromide
0.05
0.07.mu. equivalent spherical diameter
Cyan Coupler C-1 0.23
Dispersed in Solvent S-3
0.11
Oxidized Developer Scavenger SCV-1
0.03
Dispersed in Solvent S-3
0.03
Gelatin 0.86
Fourth Layer: Fast Red Sensitive Layer
Silver Iodobromide Emulsion
0.68 (as silver)
tabular emulsion (12:1 aspect ratio)
1.5% bulk iodide
spectrally sensitized with dyes SD-1 and SD-2
Silver Iodobromide Emulsion
0.12 (as silver)
0.15.mu. equivalent spherical diameter
4.8% bulk iodide
spectrally sensitized
Fine Grain Silver Bromide
0.08
0.07.mu. equivalent spherical diameter
Cyan Coupler C-1 1.36
Dispersed in Solvent S-3
0.68
Gelatin 2.15
Fifth Layer: Interlayer
Oxidized Developer Scavenger SCV-1
0.11
Dispersed in Solvent S-3
0.11
Inhibitor I-1 o.ooi
Gelatin 0.61
Sixth Layer: Interlayer
Filter Dye FD-1 0.06
Gelatin 0.61
Seventh Layer: Slow Green Sensitive Layer
Silver Iodobromide Emulsion
0.27 (as silver)
tabular emulsion (7:1 aspect ratio)
3% bulk iodide
spectrally sensitized with dyes SD-3 and SD-4
Silver Iodobromide Emulsion
0.22 (as silver)
tabular emulsion (6:1 aspect ratio)
4% bulk iodide
spectrally sensitized with dyes SD-3 and SD-4
Silver Iodobromide Emulsion
0.11 (as silver)
0.15.mu. equivalent spherical diameter
4.8% bulk iodide
spectrally sensitized
Magenta Coupler M-1 0.05
Magenta Coupler H-2 0.11
Co-dispersed in Solvent S-2
0.08
Gelatin 0.86
Eighth Layer: Fast Green Sensitive Layer
Silver Iodobromide Emulsion
0.62 (as silver)
tabular emulsion (11:1 aspect ratio)
2% bulk iodide
spectrally sensitized with dyes SD-3 and SD-4
Silver Iodobromide Emulsion
0.06 (as silver)
0.15.mu. equivalent spherical diameter
4.8% bulk iodide
spectrally sensitized
Magenta Coupler M-1 0.34
Magenta Coupler M-2 0.78
Co-dispersed in Solvent S-2
0.56
Gelatin 1.94
Ninth Layer: Interlayer
Oxidized Developer Scavenger SCV-1
0.11
Dispersed in Solvent S-4
0.03
Gelatin 0.61
Tenth Layer: Slow Blue Sensitive Layer
Silver Iodobromide Emulsion
0.48 (as silver)
tabular emulsion (13:1 aspect ratio)
2% bulk iodide
spectrally sensitized with dyes SD-5 and SD-6
Yellow Coupler YEL-1 0.48
Dispersed in Solvent S-3
0.16
Gelatin 0.86
Eleventh Layer: Fast Blue Sensitive Layer
Silver Iodobromide Emulsion
0.65 (as silver)
tabular emulsion (22:1 aspect ratio)
3% bulk iodide
spectrally sensitized with dyes SD-7 and SD-8
Yellow Coupler YEL-1 1.66
Dispersed in Solvent S-3
0.56
Gelatin 2.37
Twelfth Layer: First Protective Layer
UV Dye UV-2 0.38
UV Dye UV-3 0.07
UV Dye UV-1 0.13
Dispersed in Latex L-1 0.65
Oxidized Developer Scavenger SCV-1
0.06
Dispersed in Solvent S-3
0.56
Gelatin 2.37
Thirteenth Layer: Second Protective Layer
Fine Grain Silver Bromide
0.12 (as silver)
0.07.mu. equivalent spherical diameter
Matte 0.02
3.3.mu. spherical diameter
Hardener H-1 0.32
Gelatin 0.98
______________________________________
Samples 202, and 204-206 were prepared in the same manner as described
above for Sample 201 except that 0.22 g/m.sup.2 of the yellow filter dye
listed in Table II was added to the Ninth Layer. Sample 203 was prepared
in the same manner as described for sample 202 except that an extra
interlayer consisting of 0.61 g/m.sup.2 of gelatin was coated between the
Eighth and Ninth Layers.
Each of the samples thus prepared was cut into a 35 mm width strip. The
samples were exposed to a step exposure using white light. The samples
were then processed using standard Kodak E-6 processing solutions and
methods. The Status A blue density was measured for the Dmin step of each
sample. The samples were placed on a light box for 24 hours. The Status A
blue density was then re-measured for the Dmin step of each sample. The
density values before and after the light box treatment, and the delta
density, are tabulated in Table III.
TABLE III
______________________________________
Extra Starting
Ending Delta
Sample
Yellow Filter Dye
Interlayer
Density
Density
Density
______________________________________
201 None (Check) N 0.14 0.14 0
262 FD-2 (Companson)
N 0.19 0.27 0.08
203 FD-2 (Comparison)
Y 0.18 0.24 0.06
204 FD-3 (Comparison)
N 0.18 0.23 0.05
205 FD-4 (Comparison)
N 0.20 0.23 0.03
206 YFD-4 (Invention)
N 0.18 0.18 0
______________________________________
Compared to Sample 201 the comparison Samples 202 and 204-205 exhibit an
increased blue Dmin density after the light box treatment. Comparison
sample 203 demonstrates that the addition of an extra interlayer to create
a separation between the yellow filter dye and four-equivalent pyrazolone
magenta coupler is an ineffective means to eliminate the yellow stain
problem. Invention sample 206 demonstrates that the yellow filter dye of
the present invention eliminates any yellow stain formation.
The components employed for the preparation of light-sensitive materials
not already identified above are shown below.
##STR10##
Hardener H-1 is 1,1'-›methylenebis(sulfonyl)!bisethene Solvent S-1 is
1,4-Cyclohexylenedimethylene bis(2-ethylhexanoate)
Solvent S-2 is Phosphoric acid, tris(methylphenyl) ester
Solvent S-3 is 1,2-Benzenedicarboxylic acid, dibutyl ester
Solvent S-4 is N,N-Diethyl lauramide
The invention has been described in detail with particular reference to
preferred embodiments, but it will be understood that variations and
modifications can be effected within the spirit and scope of the
invention.
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